Proton‐Coupled Reduction of an Iron Cyanide Complex to Methane and Ammonia |
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| Authors: | Dr. Jonathan Rittle Prof. Jonas C. Peters |
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| Affiliation: | Division of Chemistry and Chemical Engineering, California Institute of Technology, USA |
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| Abstract: | Nitrogenase enzymes mediate the six‐electron reductive cleavage of cyanide to CH4 and NH3. Herein we demonstrate for the first time the liberation of CH4 and NH3 from a well‐defined iron cyanide coordination complex, [SiPiPr3]Fe(CN) (where [SiPiPr3] represents a tris(phosphine)silyl ligand), on exposure to proton and electron equivalents. [SiPiPr3]Fe(CN) additionally serves as a useful entry point to rare examples of terminally‐bound Fe(CNH) and Fe(CNH2) species that, in accord with preliminary mechanistic studies, are plausible intermediates of the cyanide reductive protonation to generate CH4 and NH3. Comparative studies with a related [SiPiPr3]Fe(CNMe2) complex suggests the possibility of multiple, competing mechanisms for cyanide activation and reduction. |
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| Keywords: | carbyne ligands cyanide cleavage iron complexes nitrogenase nitrogen fixation |
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